Nanopore characterization of mine roof shales by SANS, nitrogen adsorption, and mercury intrusion: impact on water adsorption/retention behavior

Moisture-induced reduction in the strength of shales is one of the primary mechanisms of roof degradation affecting the stability and safety of underground coal mines. The underlying mechanisms of nanoscale matrix-water interactions remains unclear. Thus, an improved understanding of the nanopore structure, and dependent water adsorption and retention behavior of shale is key in defining strength degradation due to seasonal variations in humidity and temperature in underground coal mines. We use small-angle neutron scattering (SANS), low-pressure N2 adsorption (LPNA), and high-pressure mercury intrusion porosimetry (MIP) to characterize the nanopore structure of a fireclay (7F) and four coal mine roof shales (6R, 5A, 6F, H6) from the Illinois basin. The results show that overall distributions of pore volume obtained from SANS, LPNA and MIP techniques agree well between methods and over a wide range of pore size from ~1 nm to ~100 nm. Mercury porosities for the five ordered (7F, 6R, 5A, 6F, H6) samples (7.3%, 7.8%, 8.3%, 12.3%, 4.6%) are higher than the respective N2 porosities (5.0%, 6.3%, 3.8%, 8.2%, 2.5%), as attributed to the dilation of mesopores and compression of the grain skeleton induced by high pressure intrusion of mercury. The SANS porosities for samples 7F, 6R, 5A, 6F (4.0%, 6.2%, 4.1%, 8.8%) are in good agreement with their N2 porosities. Among all tested samples, H6 shale exhibits a relatively high SANS porosity (8.0%) but the lowest N2 (2.5%) and mercury porosities (4.6%). This is attributed to the interlayer micro-pore spaces within montmorillonite, which is detected by SANS but not by the two fluid penetration methods due to the inaccessibility of N2 molecules and mercury. Based on LPNA, larger micropores (1.5–2 nm) and mesopores (2–50 nm) predominantly contribute to the total porosity (~77.8%–87.6%) for the five tested samples.